Catalysts

ABSTRACT

A method of preparing a modified catalyst support comprises contacting a catalyst support material with a modifying component precursor in an impregnating liquid medium. The impregnating liquid medium comprises a mixture of water and an organic liquid solvent for the modifying component precursor. The mixture contains less than 17% by volume water based on the total volume of the impregnating liquid medium. The modifying component precursor comprises a compound of a modifying component selected from the group consisting of Si, Zr, Co, Ti, Cu, Zn, Mn, Ba, Ni, Al, Fe, V, Hf, Th, Ce, Ta, W, La and mixtures of two or more thereof. A modifying component containing catalyst support material is thus obtained. Optionally, the modifying component containing catalyst support material is calcined at a temperature above 100° C. to obtain a modified catalyst support.

FIELD OF THE INVENTION

THIS INVENTION relates to catalysts. More particularly, it relates to amethod of preparing a modified catalyst support, to a method ofpreparing a catalyst precursor, to a method of preparing a catalyst, andto a hydrocarbon synthesis process employing the resultant catalyst.

BACKGROUND ART

Hydrocarbon synthesis from hydrogen and carbon monoxide in the presenceof a Fischer-Tropsch catalyst is commonly known as Fischer-Tropsch (FT)synthesis. FT synthesis forms part of gas-to-liquids, coal-to-liquids,and biomass-to-liquids processes in which natural gas, coal, and biomassrespectively are usually converted by means of a three step process intoliquid hydrocarbons. The three process steps are normally (i) productionof synthesis gas (or ‘syngas’) comprising a mixture of hydrogen andcarbon monoxide from natural gas, coal, or biomass respectively, (ii)conversion of the syngas into a waxy hydrocarbons or syncrude by meansof FT synthesis, and (iii) a hydrocracking or hydrotreating step toconvert the waxy syncrude into liquid transportation fuels such asdiesel, petrol, jet fuel, as well as naphtha.

During the FT synthesis described in step (ii) above the syngas in theform of CO and H₂ is contacted with a FT synthesis catalyst under FTsynthesis conditions to produce the waxy hydrocarbons. One type ofcatalyst which is often used in low temperature FT (LIFT) synthesiscomprises an active catalyst component such as Co on a catalyst supportsuch as alumina, silica, titania, magnesia or the like.

Contamination of the waxy hydrocarbon product produced during FTsynthesis with ultra fine particulate matter derived from the supportsuch as alumina, and the active catalyst component such as Co, wasexperienced. This resulted in loss of the expensive active catalystcomponent as well as fouling of the downstream processes described in(iii) above with the support and active catalyst component ultra fineparticles. It is believed that this wax product contamination is as aresult of one or both of: (a) Catalyst support dissolution duringaqueous impregnation of the catalyst support with the active catalystcomponent (during preparation of the catalyst) which may result inprecipitation and coating of the bulk support material with a physicallybonded amorphous layer of the support material whereon the activecatalyst component is deposited. This amorphous layer is insufficientlyanchored and results in dislodgement of and washing out of activecatalyst component rich ultra fine particles during FT synthesis; and(b) The FT synthesis catalyst is susceptible to hydrothermal attack thatis inherent to realistic FT synthesis conditions. Such a hydrothermalattack on exposed and unprotected support material will result incontamination of the waxy hydrocarbon product with ultra fineparticulate matter rich in the active catalyst component.

WO 99/42214, WO 02/07883, WO 03/012008 and U.S. Pat. No. 7,365,040 alldisclose modification of a FT synthesis catalyst support with amodifying component to reduce the dissolution of the catalyst support inaqueous environment, including hydrothermal attack, thereby to reducethe negative effect of ultra fine particles rich in active catalystcomponent contaminating the waxy hydrocarbon product.

WO 99/42214, WO 02/07883, and U.S. Pat. No. 7,365,040 all disclosemodification of a FT synthesis catalyst support by impregnation of thesupport with the modifying component carried in an organic solvent suchas ethanol. Water is specifically avoided in order to avoid dissolutionof the support in an aqueous environment during the support modificationprocess.

WO 2009/049280 discloses modification of a catalyst support byimpregnating the support with a modifying component carried in water. WO2009/049280 is not limited to the preparation of FT catalysts andaccordingly the problem associated with support dissolution in anaqueous medium does not play such an important role in that case. Itshould be noted that WO 2009/049280 discloses, on page 17, that when theuse of water is compared to the use of anhydrous ethanol duringimpregnation of the support with the modifying component, a lowersilicon content on the support is achieved when water is used. This isaccordingly a disadvantage associated with water as an impregnatingliquid medium.

Most surprisingly, it has now been found that when a certain mixture ofwater and an organic solvent was used to impregnate a modifyingcomponent onto a catalyst support, it may result in a higher modifyingcomponent content being deposited on the support compared to when nowater is used during impregnation. It thus resulted in betterutilisation of the modifying component. This is contrary to what isexpected from the teachings of WO 2009/049280 set out above, namely thatthe use of water instead of ethanol as an impregnating liquid mediumresulted in lower usage of the modifying component. This higher usage ofthe modifying component resulted in a higher loading of the modifyingcomponent or alternatively less wastage of the modifying component. Itis well known that a higher loading of the modifying component resultsin a lower solubility of the catalyst support in water. Surprisingly,when specified amounts of water were used in the impregnating liquidmedium, it resulted in improved attrition resistance of the modifiedcatalyst support compared to the use of only water (and in some cases ofonly ethanol) as the impregnating liquid medium.

DISCLOSURE OF THE INVENTION

According to a first aspect of the invention, there is provided a methodof preparing a modified catalyst support, the method comprising

contacting a catalyst support material with a modifying componentprecursor in an impregnating liquid medium wherein the impregnatingliquid medium comprises a mixture of water and an organic liquid solventfor the modifying component precursor, which mixture contains less than17% by volume water based on the total volume of the impregnating liquidmedium, and the modifying component precursor comprises a compound of amodifying component selected from the group consisting of Si, Zr, Co,Ti, Cu, Zn, Mn, Ba, Ni, Al, Fe, V, Hf, Th, Ce, Ta, W, La and mixtures oftwo or more thereof, thereby to obtain a modifying component containingcatalyst support material; and

optionally, calcining the modifying component containing catalystsupport material at a temperature above 100° C. to obtain a modifiedcatalyst support.

It will be appreciated that, in one embodiment of the invention, nocalcination above 100° C. of the modifying component containing catalystsupport material takes place so that the non-calcined modifyingcomponent containing catalyst support material then constitutes themodified catalyst support. In other words, a non-calcined modifiedcatalyst support is then produced.

In an alternative embodiment of the invention, calcination above 100° C.of the modifying component containing catalyst support material takesplace to provide the modified catalyst support in the form of a calcinedmodified catalyst support.

According to a second aspect of the invention, there is provided amethod of preparing a catalyst precursor, the method comprising

contacting a catalyst support material with a modifying componentprecursor in an impregnating liquid medium wherein the impregnatingliquid medium comprises a mixture of water and an organic liquid solventfor the modifying component precursor, which mixture contains less than17% by volume water based on the total volume of the impregnating liquidmedium, and the modifying component precursor comprises a compound of amodifying component selected from the group consisting of Si, Zr, Co,Ti, Cu, Zn, Mn, Ba, Ni, Al, Fe, V, Hf, Th, Ce, Ta, W, La and mixtures oftwo or more thereof, thereby to obtain a modifying component containingcatalyst support material;

optionally, calcining the modifying component containing catalystsupport material at a temperature above 100° C. to obtain a modifiedcatalyst support; and

introducing a precursor compound of an active catalyst component ontoand/or into (i) the catalyst support material prior to contacting thecatalyst support material with the modifying component precursor; (ii)the modifying component containing catalyst support material; and/or(iii) the modified catalyst support, thereby to obtain a catalystprecursor.

It will be appreciated that in one embodiment of the invention nocalcination above 100° C. of the modifying component containing catalystsupport material takes place so that the non-calcined modifyingcomponent containing catalyst support material then constitutes themodified catalyst support. In other words, a non-calcined modifiedcatalyst support is then produced.

In an alternative and preferred embodiment of the invention, calcinationabove 100° C. of the modifying component containing catalyst supportmaterial takes place to provide the modified catalyst support in theform of a calcined modified catalyst support.

It will be appreciated that when the precursor compound of the activecatalyst component is introduced onto and/or into the modified catalystsupport it may be onto and/or into the non-calcined modified catalystsupport or the calcined modified catalyst support. Preferably the activecatalyst component is introduced onto and/or into the calcined modifiedcatalyst support.

The Impregnating Liquid Medium

The impregnating liquid medium thus contains less than 17% by volumewater. Preferably, however, the impregnating liquid medium contains lessthan 12% by volume water; preferably not more than 10% by volume water.Preferably, the impregnating liquid contains at least 0.4% by volumewater, preferably more than 0.4% by volume water, preferably at least2.5% by volume water, preferably at least 3% by volume water.

The organic liquid solvent may comprise a liquid organic compound whichincludes at least one heteroatom selected from oxygen or nitrogen. Whenthe heteroatom is oxygen, it may be part of an oxygen containing groupselected from an alcohol, a ketone, an aldehyde, an ether, an ester, aglycol, an acid (including an organic acid) and a mixture of two or morethereof. Preferably the oxygen containing liquid organic compound is analcohol, and preferably it is C1 to C10 alcohol, preferably a C1 to C3alcohol. Preferably the alcohol includes a single OH group andpreferably the alcohol is ethanol. Alternatively the oxygen containingliquid organic compound may be selected from the group consisting ofethyl acetate and acetone. When the heteroatom is nitrogen, the nitrogencontaining organic compound may be acetonitrile. The organic liquidsolvent may comprise a mixture of organic compounds, preferably amixture of organic compounds as described above.

In one embodiment of the invention, the organic liquid solvent may be apolar solvent. In one embodiment of the invention, the organic liquidsolvent may have a boiling point of not more than 97° C., preferably notmore than 80° C.

The Catalyst Support Material

The catalyst support material that is contacted with the modifyingcomponent precursor may be selected from the group consisting of acatalyst support precursor which is convertible to a catalyst supportupon calcination thereof; and a catalyst support.

When the catalyst support material is a catalyst support precursor, itmay be a compound which, upon calcination, converts to a catalystsupport in the form of an oxide, preferably a metal oxide. Preferably,the metal oxide is an oxide of a metal selected from the groupconsisting of Al, Si, Ti, Mg, Zr and Zn. More particularly, the catalystsupport precursor may then comprise an aluminium compound which convertsto one or more aluminium oxides upon calcination. Preferably, thealuminium compound is Al(OH)₃, such as gibbsite and/or bayerite and/orAlO(OH), and more preferably it is boehmite. The catalyst supportprecursor may be shaped into particulate form after the introduction ofthe modifying component precursor onto and/or into the catalyst supportprecursor and before calcination thereof. The shaping may, for example,be carried out by means of spray drying. Prior to shaping the catalystsupport precursor, it may be partially dried. The resulting shapedproduct may then be subject to the calcination above 400° C. Thiscalcination preferably takes place prior to introducing the catalystprecursor compound onto and/or into the shaped product. In order toachieve a desired particle size distribution, classification may beperformed on the shaped particulate product, using, for example,cyclones or sieves.

However, the catalyst support material is preferably a catalyst support.The catalyst support may then be any catalyst support suitable forsupporting thereon the active catalyst component or a precursor compoundof the active catalyst component. The catalyst support is preferablysuitable for use as a support in a catalyst for synthesisinghydrocarbons and/or oxygenates of hydrocarbons from at least hydrogenand carbon monoxide, particularly a Fischer-Tropsch (FT) synthesiscatalyst. The FT synthesis catalyst may be for use in a process to beperformed in a fixed bed reactor, slurry bed reactor or even a fixedfluidized bed reactor. Preferably, the process is to be performed in athree phase slurry bed FT synthesis reactor.

The catalyst support is usually a porous support, and preferably it isalso preshaped. The porous support preferably has an average porediameter from 8 to 50 nanometers, more preferably from 10 to 15nanometers. The pre-shaped support may be a particulate support,preferably with an average particle size of from 1 to 500 micrometers,more preferably from 10 to 250 micrometers, and still more particularlyfrom 45 to 200 micrometers.

The catalyst support may be selected from the group consisting ofalumina in the form of one or more aluminium oxides; silica (SiO₂);titania (TiO₂); magnesia (MgO); zirconium oxide (ZrO₂), zinc oxide(ZnO); and mixtures thereof. Preferably, the support is selected fromthe group consisting of alumina in the form of one or more aluminiumoxides and titania (TiO₂). More preferably, the support is alumina inthe form of one or more aluminium oxides.

The one or more aluminium oxides may be selected from the groupincluding (preferably consisting of) gamma alumina, theta alumina and amixture of two or more thereof. Preferably the group includes, or, morepreferably, consists of, gamma alumina, theta alumina and a mixture ofgamma alumina and theta alumina. The aluminium oxide catalyst supportmay be that obtainable under the trademark Puralox, preferably PuraloxSCCa 150, from SASOL Germany GmbH. Puralox SCCa 150 is a spray-driedaluminium oxide support consisting of a mixture of gamma and thetaaluminium oxide.

The aluminium oxide may be a crystalline compound which can berepresented by the formula Al₂O₃.xH₂O where 0<x<1. The term ‘aluminiumoxide’ thus excludes Al(OH)₃, and AlO(OH), but includes compounds suchas gamma, delta and theta alumina.

The Modifying Component Precursor

The modifying component precursor may comprise an inorganic compound ofthe modifying component. Preferably however, the modifying componentprecursor includes one or more organic groups bound to the modifyingcomponent. Preferably one or more, but preferably all, organic groupsare bound to the modifying component via an oxygen atom. Preferably allthe groups bound to the modifying component are organic groups andpreferably all said organic groups are bound to the modifying componentvia an oxygen atom.

In a preferred embodiment of the invention some, but preferably all, theorganic groups are of the formula —(O)—R where R is an organic group. Rmay be an acyl, an aryl, an heteroaryl, a cyclic compound (including aheterocyclic compound) or a hydrocarbyl group, preferably a hydrocarbylgroup, preferably an alkyl group, preferably an alkyl group with notmore than ten carbon atoms, and preferably an alkyl group with not morethan three carbon atoms. Alternatively, R may be of the formula —OR¹where R¹ may be a hydrocarbyl group, preferably an alkyl group,preferably an alkyl group with not more than ten carbon atoms, andpreferably an alkyl group with not more than three carbon atoms.

The modifying component may be selected from the group consisting of Si,Zr, Ti, Cu, Zn, Mn, Ba, Ni, Al, V, W, La and mixtures of two or morethereof.

Preferably the modifying component is selected from the group consistingof Si, Ti and Zr.

In a preferred embodiment of the invention, the modifying component isSi. Preferably the modifying component precursor is then an organicsilicon compound, preferably of the formula Si(OR)₄ where R is anorganic group. Preferably R is an alkyl or acyl group. Preferably themodifying component precursor is then tetra ethoxy silane (TEOS) ortetra methoxy silane (TMOS).

In another embodiment of the invention, the modifying component may beZr. The modifying component precursor may then be an organic zirconiumcompound, preferably of the formula Zr(OR)₄ where R is an organic group.Preferably R is an alkyl or acyl group. Preferably the modifyingcomponent precursor is then a zirconium alkoxide, for example zirconiumisopropoxide (Zr(OCH(CH₃)₂)₄.

In yet another embodiment of the invention, the modifying component maybe Ti. The modifying component precursor may then be an organic titaniumcompound, preferably of the formula Ti(OR)₄ where R is an organic group.Preferably R is an alkyl or acyl group. Preferably the modifyingcomponent precursor is then a titanium alkoxide, for example titaniumtetrabutoxide.

Contacting of the Catalyst Support Material with the Modifying ComponentPrecursor

By contacting the catalyst support material with the modifying componentprecursor in the impregnating liquid medium, the modifying componentprecursor is thus introduced into and/or onto the catalyst supportmaterial by means of impregnation. The impregnation may be incipientwetness impregnation, but preferably it is slurry phase impregnation.

The impregnation by means of the impregnating liquid medium ispreferably carried out at a temperature above 25° C. The temperature maybe at or near the boiling point of the impregnating liquid medium. Theimpregnation may be carried out for a period from 1 minute to 20 hours,preferably from 1 minute to 5 hours. The impregnation may be effected atatmospheric pressure.

After impregnation the excess impregnating liquid medium may be removed,preferably at sub-atmospheric conditions, preferably from 0.01 to 0.1bar(a). The removal is preferably carried out at temperature above 25°C., preferably at or near the boiling point of the impregnating liquidmedium.

During impregnation, sufficient impregnating liquid medium may thus beused to cause conditions of incipient wetness, alternatively conditionsof slurry impregnation.

Optional Calcination of the Modifying Component Containing CatalystSupport Material

This calcination, when employed, is thus effected at a temperature above100° C., preferably at a temperature of at least 150° C. preferably atleast 450° C. Where the modifying component is Si, the calcination ispreferably not effected at a temperature above 550° C. The calcinationmay be for a period from 1 minute to 12 hours, preferably from 10minutes to 4 hours.

The calcination may be effected in a non-reducing gas, preferably in anoxygen containing gas, preferably in air.

Preferably the calcination results in decomposition of the modifyingcomponent precursor. Preferably, during calcination the modifyingcomponent precursor is converted to an oxide of the modifying component.

Introducing the Precursor Compound of the Active Catalyst Component

The active catalyst component may be a known component active forhydrocarbon synthesis process (preferably a FT synthesis process), andmay be selected from the group consisting of cobalt (Co), iron (Fe),nickel (Ni) and ruthenium (Ru). Cobalt (Co) is preferred.

The precursor compound may thus be any suitable compound of the activecatalyst component. Preferably, it is an inorganic compound, morepreferably an inorganic salt of the active catalyst component. Thecatalyst precursor compound may be cobalt nitrate, and particularly itmay be Co(NO₃)₂.6H₂O.

The precursor compound may be introduced by any suitable manner, butpreferably it is by means of impregnation. Preferably, the modifiedcatalyst support or the catalyst support material is impregnated withthe catalyst precursor compound by forming a mixture of the precursorcompound; a liquid carrier for the precursor compound; and the modifiedcatalyst support or the catalyst support material.

The liquid carrier may comprise a solvent for the precursor compound andpreferably the precursor compound is dissolved in the liquid carrier.The liquid carrier may be water.

The impregnation may be effected by any suitable impregnation method,including incipient wetness impregnation or slurry phase impregnation.Slurry phase impregnation is preferred. Preferably, the precursorcompound is dissolved in the liquid carrier in order that the volume ofthe solution is greater than xy liter, which solution is then mixed withthe modified catalyst support or the catalyst support material, andwherein x is the BET pore volume of the modified catalyst support or thecatalyst support material in I/kg support, and y is the mass of modifiedcatalyst support or catalyst support material to be impregnated in kg.Preferably the volume of the solution is greater than 1.5xy liter, andpreferably it is about 2xy liter.

The impregnation may be carried out at sub-atmospheric pressure,preferably below 85 kPa(a), preferably at 20 kPa(a) and lower.Preferably the impregnation is also carried out at a temperature above25° C. The impregnation temperature may be above 40° C., preferablyabove 60° C., but preferably not above 95° C.

The impregnation may be followed by partial drying of the impregnatedsupport, preferably at a temperature above 25° C. The drying temperaturemay be above 40° C., preferably above 60° C., but preferably not above95° C. Preferably the partial drying may be effected at sub-atmosphericconditions, preferably below 85 kPa(a), preferably at 20 kPa(a) orlower.

In one embodiment of the invention, the impregnation and partial dryingof the modified catalyst support or the catalyst support material may becarried out using a procedure which includes a first step wherein themodified catalyst support or the catalyst support material isimpregnated (preferably slurry impregnated) with the precursor compoundat a temperature above 25° C., and at sub-atmospheric pressure, and theresultant product is dried; and at least one subsequent step wherein theresulting partially dried impregnated modified catalyst support orcatalyst support material of the first step is subjected to treatment ata temperature above 25° C., and sub-atmospheric pressure such that thetemperature of the subsequent step exceeds that in the first step and/orthe sub-atmospheric pressure in the subsequent step is lower than thatin the first step. This two step impregnation procedure may be asdescribed in WO 00/20116, which is incorporated herein by reference.

A dopant capable of enhancing the reducibility of the active catalystcomponent may also be introduced onto and/or into the modified catalystsupport or the catalyst support material. The dopant may be introducedduring or after the introduction of the catalyst precursor compound ontoand/or into the modified catalyst support or the catalyst supportmaterial. The dopant may be introduced as a dopant compound which is acompound of a metal selected from the group including palladium (Pd),platinum (Pt), ruthenium (Ru), rhenium (Re) and a mixture of two or morethereof. Preferably, the dopant compound is an inorganic salt, and it ispreferably soluble in water. The mass proportion of the metal of thedopant to the active catalyst component metal may be in the ratio of0.01:100 to 3:100.

The partially dried catalyst support with the catalyst precursorcompound thereon and/or therein may be calcined. The calcination may beeffected in order to decompose the catalyst precursor compound and/orcausing it to react with oxygen. For example, cobalt nitrate may beconverted into a compound selected from CPO, CoO(OH), Co₃O₄, Co₂O₃ or amixture of two or more thereof.

The calcination may be carried out in any suitable manner such as in arotary kiln, but preferably it is carried out in a fluidised bedreactor.

The calcination may be carried out in an inert atmosphere, butpreferably it is carried out in the presence of oxygen, more preferablyin air.

Preferably the calcination is carried out at a temperature above 95° C.,more preferably above 120° C., still more preferably above 200° C., butpreferably not above 400° C., more preferably not above 300° C. This isespecially the case where Co is the active catalyst component.

The calcination may be carried out by using a heating rate and an airspace velocity that comply with the following criteria:

-   -   (i) when the heating rate is ≦1° C./min, the air space velocity        is at least 0.76 m_(n) ³/(kg Co(NO₃)₂.6H₂O)/h; and    -   (ii) when the heating rate is higher than 1° C./min, the air        space velocity satisfies the relation:

${\log\mspace{14mu}\left( {{space}\mspace{14mu}{velocity}} \right)} \geq {{\log\mspace{20mu} 0.76} + {\frac{{\log\mspace{14mu} 20} - {\log\mspace{14mu} 0.76}}{2}\log\mspace{14mu}\left( {{heating}\mspace{14mu}{rate}} \right)}}$

The above conditions for air space velocity and heating rate areespecially applicable where Co is the active catalyst component.

The impregnation, the partial drying and calcination may be repeated toachieve higher loadings of the catalyst precursor compound on thecatalyst support or the catalyst support material. In one embodiment ofthe invention, a first impregnation, drying and calcination proceduremay be followed by a partial reduction procedure of the calcinedmaterial; and the partially reduced material may then be subjected to afurther impregnation, drying and calcination procedure. The partialreduction procedure may be executed with a final temperature of between100° C. and 300° C., especially in the case where Co is the activecatalyst component.

In one embodiment of the invention, the catalyst precursor may beprepared by a method which includes, in a first preparation step,impregnating the modified catalyst support or the catalyst supportmaterial with an organic metal compound of the active catalyst componentin a carrier liquid, at least partially drying the impregnated supportor support material, and calcining the at least partially driedimpregnated support or support material, to obtain a calcinedintermediate; and in a second preparation step, impregnating thecalcined intermediate from the first impregnation step, with aninorganic metal salt of the active catalyst component in a carrierliquid, at least partially drying the impregnated support, and calciningthe at least partially dried impregnated support, to obtain the catalystprecursor. The organic metal compound may be an organic cobalt compound.

The catalyst precursor may have reduced dissolution in an aqueousenvironment, preferably an acidic aqueous environment.

Catalyst

According to a third aspect of the invention, there is provided a methodof preparing a catalyst, which includes preparing a catalyst precursorusing the method of the second aspect of the invention; and reducing thecatalyst precursor, thereby activating the catalyst precursor andobtaining the catalyst. The reduction of the catalyst precursorpreferably includes treating it with a reducing gas to activate it.Preferably, the reducing gas is hydrogen or a hydrogen containing gas.The hydrogen containing gas may consist of hydrogen and one or moreinert gases which are inert in respect of the active catalyst. Thehydrogen containing gas preferably contains at least 90 volume %hydrogen.

The reducing gas may be contacted with the catalyst precursor in anysuitable manner. Preferably the catalyst precursor is provided in theform of a bed with the reducing gas being caused to flow through the bedof particles. The bed of particles may be a fixed bed, but preferably itis a fluidised bed and preferably the reducing gas acts as thefluidising medium for the bed of catalyst precursor particles.

The reduction may be carried out at a pressure from 0.6 to 1.5 bar(a),preferably from 0.8 to 1.3 bar(a). Alternatively the pressure may befrom 1.5 bar(a) to 20 bar(a). Preferably, however, the pressure is atabout atmospheric pressure.

The reduction is preferably carried out at a temperature in excess of25° C. above that at which the catalyst precursor will be reduced to anactive form. Preferably, the activation is carried out at a temperatureabove 150° C., and preferably below 600° C., especially where the activecatalyst component is cobalt. Preferably the reduction is carried out ata temperature below 500° C., more preferably below 450° C.

During activation the temperature may be varied, and preferably it isincreased to a maximum temperature as set out above.

The flow of the reducing gas through the catalyst bed is preferablycontrolled to ensure that contaminants produced during reduction aremaintained at a sufficiently low level. The reducing gas may berecycled, and preferably the recycled reducing gas is treated to removeone or more contaminants produced during reduction. The contaminants maycomprise one or more of water and ammonia.

The activation may be carried out in two or more steps during which oneor both of the heating rate and the space velocity of the reducing gasis varied.

In one embodiment of the invention, the active catalyst may be coated byintroducing a mixture of active catalyst particles and a coating mediumin the form of molten organic substance, which is at a temperature T₁,and which sets or congeals at a lower temperature T₂ so that T₂<T₁, intoat least one mould; and at least partly submerging the mould in acooling liquid, so as to cool the organic substance down to atemperature T₃, where T₃≦T₂.

During the activation the water partial pressure is preferably kept aslow as possible, more preferably below 0.1 atmosphere. The hydrogenspace velocity may be from 2 to 4 liters per hour per gram of catalyst.

Hydrocarbon Synthesis

According to a fourth aspect of the present invention, there is provideda hydrocarbon synthesis process which comprises preparing a catalystusing the process of the third aspect of the invention; and contactinghydrogen with carbon monoxide at a temperature above 100° C. and apressure of at least 10 bar with the catalyst so prepared, to producehydrocarbons and, optionally, oxygenates of hydrocarbons.

The temperature may be from 180° C. to 250° C., more preferably from210° C. to 240° C. The pressure more preferably may be from 10 bar to 70bar.

Preferably, the hydrocarbon synthesis process is a Fischer-Tropschprocess, more preferably a three phase Fischer-Tropsch process, stillmore preferably a slurry bed Fischer-Tropsch process for producing a waxproduct.

The hydrocarbon synthesis process may also include a hydroprocessingstep for converting the hydrocarbons and, optionally, oxygenates toliquid fuels and/or chemicals.

The present invention extends also to products produced by thehydrocarbon synthesis process of the fourth aspect of the invention.

The invention will now be described in more detail with reference to thedrawings and the following non-limiting examples:

FIG. 1 shows, for Example 13, the Si-utilisation for Si modification ofPuralox SCCa-2/150, as a function of the water concentration during themodification procedure;

FIG. 2 depicts, for Example 13, the Delta D₁₀ values as a function ofthe water concentration during the silicon modification procedure of thePuralox SCCa-5/150;

FIG. 3 shows, for Example 14, the cumulative Al dissolution as afunction of time for Si modified catalyst support materials not applyingwater addition, as well as applying water addition; and

FIG. 4 shows, for Example 37, the cumulative Al dissolution as afunction of time for the modified catalyst support materials ofExamples, 12, 23, 24, 29 and 30.

EXAMPLES Example 1 Inventive

Gamma alumina Puralox SCCa-5/150 was modified with Si, using TEOS (tetraethoxy silane) in a mixture of water and ethanol as an impregnatingliquid medium. TEOS was added to the solvent mixture of ethanol andwater (see Table 1) and stirred for 10 minutes at 60° C. PuraloxSCCa-5/150 (50 g) was added to this mixture and stirred for another 10minutes at 60° C. The impregnating liquid medium was slowly removedwhile gradually decreasing the pressure from atmospheric pressure to 80mbar(a) and maintaining it at 80 mbar(a) until dryness, while thetemperature was maintained at 60° C. By means of calcination at 510° C.for 2 hours in air, the resultant modifying component containingcatalyst support material was thus converted to a calcined modifiedcatalyst support.

Example 2 Inventive

A modified catalyst support, as described in Example 1, was prepared,but with 2.5 vol % water in the total solvent mixture, i.e. in theimpregnating liquid medium (see Table 1).

Example 3 Inventive

A modified catalyst support, as described in Example 1, was prepared,but with 6 vol % water in the total solvent mixture (see Table 1).

Example 4 Inventive

A modified catalyst support, as described in Example 1, was prepared,but with 7.5 vol % water in the total solvent mixture (see Table 1).

Example 5 Inventive

A modified catalyst support, as described in Example 1, was prepared,but with 11 vol % water in the total solvent mixture (see Table 1).

Example 6 Comparative

A modified catalyst support, as described in Example 1, was prepared,but with 17 vol % water in the total solvent mixture (see Table 1).

Example 7 Comparative

A modified catalyst support, as described in Example 1, was prepared,but with 47 vol % water in the total solvent mixture (see Table 1).

Example 8 Comparative

A modified catalyst support, as described in Example 1, was prepared,but with 96 vol % water in the total solvent mixture (see Table 1).

Example 9 Inventive

A modified catalyst support, as described in Example 1, was prepared,but with 6 vol % water in the total solvent mixture (see Table 1).

Example 10 Comparative

A modified catalyst support, as described in Example 1, was prepared,but using ethanol only as solvent (i.e. no water was used).

Example 11 Comparative

A modified catalyst support, as described in Example 1, was prepared,but using water only as solvent (i.e. no ethanol was used).

Example 12 Comparative

The gamma alumina Puralox SCCa-5/150, was not modified at all.

Example 13

The silicon content of some of the modified catalyst supports wasdetermined by means of ICP (Inductive Coupled Plasma) analysis. Thesilicon utilisation was calculated by dividing the silicon content asanalysed by the silicon content that was aimed for, and multiplied by100 (see results in Table 1 and FIG. 1).

The D₁₀ attrition index, a single impact test, was utilized toinvestigate the physical strength of the silica modified supports. TheD₁₀ attrition index is determined by using a Malvern Digisizer 2000.During analysis particles are impinged onto a steel plate and the amountof breakage gives an indication of the physical strength of theparticles. ±2.5 g of sample was used for each analysis. To determine theD₁₀ value, two measurements are required, one at an air pressure settingof 0.15 bar and one at an air pressure setting of 3.0 bar. The D₁₀attrition index value is calculated by subtracting the D₁₀ value at anair pressure of 3.0 bar from the D₁₀ value at an air pressure of 0.15bar (see results in Table 1 and FIG. 2). The D₁₀ attrition index is anindication of the attrition resistance—the lower the value, the betteris the attrition resistance.

TABLE 1 Si-utilisation and Delta D₁₀ Values of modified catalystsupports. Si- EtOH Water TEOS Target utilisation Delta Support name (ml)(vol %) (g) % Si (%)^(a) D₁₀ ^(b) Ex 1 50 0.4 8.05 2.1 80 2.7(inventive) Ex 2 50 2.5 8.05 2.1 84 3.1 (inventive) Ex 3 50 6 7.2 1.9597 3.2 (inventive) Ex 4 50 7.5 8.05 2.1 83 3.6 (inventive) Ex 5 50 118.05 2.1 85 4.5 (inventive) Ex 6 50 17 8.05 2.1 78 6.3 (comparative) Ex7 26 47 7.2 1.95 97 6.3 (comparative) Ex 8 5 96 7.2 1.95 54 8(comparative) Ex 9 50 6 8.05 2.1 87 4.5 (inventive) Ex 10 50 0 7.2 1.9580 4.2 (comparative) Ex 11 0 100 8.05 2.1 27 11.2 (comparative) Ex 12 00 0 0 0 7.5 (comparative) ^(a)Determined from ICP results ^(b)Error ± 1unit

It was found that the addition of low amounts of water to the ethanolduring the impregnation of TEOS onto the catalyst support materialaccording to the present invention resulted in Si-utilisation of atleast 80% and usually above the Si-utilisation of a a support with nowater addition during the support modification process—see FIG. 1 andTable 1.

Furthermore, the addition of low amounts of water according to thepresent invention also resulted in improved Si-utilisation compared toexamples where very high volumes of water (comparative Example 8 andExample 11) and not according to the present invention were used.

Surprisingly, it was found that with the increased Si-utilisation, aconsequence of the water addition to the support modification process,the physical strength or attrition resistance of the supports increased(despite the use of water during the modification process) as seen inthe decrease in the Delta D₁₀ values, indicating a lower tendency forbreak-up of the modified catalyst support (FIG. 2).

However, the Delta D₁₀ values of the modified catalyst support graduallyincreased with higher water content in excess of 11 vol %. At a watercontent of 17 vol % the Delta D₁₀ values increased to D₁₀=6.3, showingno attrition resistance benefits in modifying the catalyst supportmaterial with silica, as Puralox SCCa-5/150, exhibited D₁₀=7.5. Thus thephysical strength of the supports decreased showing higher tendency forbreak-up with increased water content at or above 17 vol %, asillustrated in FIG. 2. A further increase in water addition to 96%(Example 8) and using water only (Example 11) had a significant negativeimpact on the attrition resistance of the silica modified catalystsupport, as can be seen from the high Delta D₁₀, at 8 and 11respectively. In the presence of excess water two distinct phases couldbe observed, due to the immiscible nature of the TEOS and the water.

Example 14 Conductivity Measurements

Alumina dissolves in an aqueous medium at low pH. The dissolution ofalumina results in the formation of aluminium ions. As more and morealumina dissolves, the concentration of aluminium increases with time.An increase in aluminium with time was followed by monitoring theconductivity at a constant pH of 2. The pH was kept constant byautomated addition of a 10% nitric acid solution.

FIG. 3 shows the cumulative Al dissolution as a function of time for Simodified catalyst support materials not applying water addition (Example10), as well as applying water addition (Example 5 and Example 9).

It can be seen that the modified support material with no wateraddition, dissolved faster compared to the modified support materialwith the addition of water during the modification step.

Example 15 Inventive

A modified catalyst support, as described in Example 1 was prepared. Thewater content in the total solvent mixture was 6 vol %, while theethanol was replaced with ethyl acetate.

Example 16 Inventive

A modified catalyst support, as described in Example 1 was prepared. Thewater content in the total solvent mixture was 6 vol %, while theethanol was replaced with acetone.

Example 17 Inventive

A modified catalyst support, as described in Example 1 was prepared. Thewater content in the total solvent mixture was 6 vol %, while theethanol was replaced with acetonitrile.

Example 18 Inventive

D₁₀ attrition index values of the modified support samples withdifferent organic solvents at 6 vol % water were determined (in the samemanner as in Example 13) and are shown in Table 2.

TABLE 2 The Delta D₁₀ values of the modified catalyst supports preparedusing different solvents. Solvent Water TEOS Target Delta Support name(50 ml) (vol %) (g) % Si D₁₀ ^(a) Ex 3 Ethanol 6 7.2 1.95 3.2(inventive) Ex 15 Ethyl 6 7.2 1.95 4.6 (inventive) acetate Ex 16 Acetone6 7.2 1.95 3.6 (inventive) Ex 17 Acetonitrile 6 7.2 1.95 4.8 (inventive)^(a)Error ± 1 unit

As can be seen from Table 2, the change in solvent did not significantlyinfluence the Delta D₁₀ value of the modified catalyst support.

Example 19 Inventive

Puralox SCCa-5/150 was evacuated to remove air from the pores. Onto thismaterial, Puralox SCCa-5/150 (100 g), a mixture of water (1.43 ml),ethanol (28.6 ml) and TEOS (16.1 g) was impregnated (using the incipientwetness technique), targeting 6 vol % water and Si-loading of 2%. Themixture was stirred at 60° C. for 10 minutes until a free flowing powderwas obtained. The resulting material was slowly dried by graduallydecreasing the pressure from atmospheric pressure to 80 mbar(a) andmaintaining it at 80 mbar(a), while the temperature was maintained at60° C. By means of calcination at 510° C. for 2 hours in air, thecatalyst support material was converted to a modified catalyst support.

The Delta D₁₀ attrition index values of the modified support samplesusing slurry and incipient wetness impregnation were determined (seeTable 3).

TABLE 3 The Delta D₁₀ values of the modified catalyst supports preparedusing slurry and incipient wetness impregnation. Solvent Water TEOSTarget Delta Support name (ml) (vol %) (g) % Si D₁₀ ^(a) Ex 9 inventive50 6 8.05 2.1 4.5 (slurry impregnation) Ex 19 Inventive 28.6 6 8.05 2.14.6 (incipient wetness impregnation) ^(a)Error ± 1 unit

The change in impregnation method did not influence the attritionresistance of the support, as indicated by the similar Delta D₁₀ valuesfor the modified catalyst supports.

Example 20 According to Invention

A cobalt based Fischer-Tropsch synthesis catalyst precursor with thecomposition 30 gCo/0.075 gPt/100 gSupport was prepared on a modifiedcatalyst support. The modified catalyst support was prepared asdescribed in Example 1, with 5 vol % water in the total solvent mixturecontaining 1.6 wt % Si, with 90% Si-utilisation.

The catalyst precursor was prepared as follows: In a first impregnationstage, Co(NO₃)₂.6H₂O (39.5 g) and [Pt(NH₄)₄(NO₃)₂] (0.0248 g) weredissolved in 50 ml of distilled water. To the mixture, 50 g of theSi-modified support was added and the water was driven off by adoptingthe drying profile shown in Table 4. Once dry, the sample was calcinedat 250° C. using a fluidised bed with a flow of air for 6 hours. Then,in a second impregnation stage, the above steps were repeated usingCo(NO₃)₂.6H₂O (28.4 g) and [Pt(NH₄)₄(NO₃)₂] (0.0407 g) dissolved in 50ml of distilled water, and to which 50 g of the calcined material fromthe first impregnation stage were added; thereafter, a similar dryingprofile as tabled in Table 4 below was adopted to dry the sample. Thedry material was then calcined at 250° C. for another 6 hours in thesame manner as for the first impregnation stage.

TABLE 4 Pressure/ Temperature/ Duration/ mbar ° C. min Atm 60 10 260 6030 260 75 90 260 85 60 50 85 180

Example 21 Comparative

A cobalt based Fischer-Tropsch synthesis catalyst precursor was preparedin the same manner as in Example 20, however, onto the modified catalystsupport according to Example 10.

Example 22

Cobalt catalyst precursors of Examples 20 and 21 were reduced prior toFischer-Tropsch synthesis in a tubular reactor at a hydrogen spacevelocity of 200 ml_(n)hydrogen/g_(catalyst)h and atmospheric pressure.The temperature was increased to 425° C. at 1° C./min, after whichisothermal conditions were maintained for 16 hours.

Between 10 g and 30 g of the resultant reduced catalyst, ranging between38 μm to 150 μm, was suspended in 300 ml molten wax and loaded in a CSTRwith an internal volume of 500 ml, under a nitrogen blanket.

The pressure was increased to 18 bar and the temperature to 230° C.,where after the synthesis was introduced. The synthesis feed gasconsisted of hydrogen and carbon monoxide, and contained 10% argon as aninternal standard. This reactor was electrically heated and sufficientlyhigh stirrer speeds were employed so as to eliminate any gas-liquid masstransfer limitations. The feed flow was controlled by means of Brooksmass flow controllers, and space velocities ranging from 2 and 4 m³_(n)/kg_(catalyst)h were used.

Further details about the experimental conditions for theFischer-Tropsch synthesis process and the FT performance after 8 dayson-line are presented in Table 5.

TABLE 5 The experimental conditions for the Fischer-Tropsch synthesisprocess and the FT performance after 8 days on-line. Ex 20 Ex 21(inventive) (comparative) Modified catalyst 5 vol % water, No water,support targeted 1.7 wt % Si, targeted 1.95 wt % Si, containing 1.6 wt %Si, containing 1.6 wt % Si, 90% Si-utilisation. 80% Si-utilisation Timeon-line (days) 8 8 Reactor pressure 18.1 18.4 (bar) Reactor temperature230 230 (° C.) Clean syngas with 1.6 1.6 H₂/CO-ratio Reactor PartialPressures (bar) H₂ 4.7 4.8 CO 3.9 4.2 H₂O 4.3 4.3 Syngas conversion 6160 (%) Activity (relative 1.0 1.0 to example 21) CH₄ selectivity 6.1 6.2(C-atom %)

It can be seen from Table 5 that the Fischer-Tropsch performance of thecatalyst containing the TEOS/ethanol/water modified catalyst support(Example 20) is comparable to the catalyst containing the TEOS/ethanolmodified catalyst support (Example 21). Due to the increased siliconutilisation, a consequence of the water addition, the targeted TEOS waslowered, i.e. less TEOS was added, to effect similar Si loadings, whichin-turn did not negatively influence FT performance of the catalyst.

In general, the examples have thus shown that support modification canbe improved by using water/organic solvent mixtures with not more than20% water, which improved the mechanical strength and the Si utilisationof the support, without affecting the FT performance.

Example 23 Comparative

Gamma alumina Puralox SCCa-150 (B31624) was modified with Ti, usingTi(O^(t)Bu)₄ (titanium tetrabutoxide) dissolved in a solvent mixture(impregnating liquid medium) of ethanol and 19 vol % acetic acid.Ti(O^(t)Bu)₄ was added to the solvent mixture (see Table 6) and stirredfor 10 minutes at 60° C. Puralox SCCa-150 (B31634) was added to thismixture and stirred for another 10 minutes at 60° C. The solvent mixturewas slowly removed with a gradual decrease of the pressure fromatmospheric pressure to 80 mbar and maintaining it at 80 mbar untildryness, while the temperature was maintained at 60° C. By means ofcalcination at 550° C. for 2 hours in air, the resultant modifyingcomponent containing catalyst support material was thus converted to acalcined modified catalyst support.

Example 24 Inventive

A modified catalyst support as described in Example 23, was prepared,but with 5 vol % water in the total solvent mixture, i.e. in theimpregnating liquid medium which thus comprised ethanol, acetic acid andwater (see Table 6).

Example 25 Comparative

A modified catalyst support as described in Example 23, was prepared,but with TEOS (tetraethoxy silane) instead of Ti(O^(t)Bu)₄ as themodifying agent (see Table 6).

Example 26 Inventive

A modified catalyst support as described in Example 25, was prepared,but with 5 vol % water in the total solvent mixture, i.e. in theimpregnating liquid medium which thus comprised ethanol, acetic acid andwater (see Table 6).

Example 27 Comparative

A modified catalyst support as described in Example 23, was prepared,but with Zr(O^(i)Pr)₃ (zirconium isopropoxide) instead of Ti(O^(t)Bu)₄as the modifying agent (see Table 6).

Example 28 Inventive

A modified catalyst support as described in Example 27, was prepared,but with 10 vol % water in the total solvent mixture i.e. in theimpregnating liquid medium which thus comprised ethanol, acetic acid andwater (see Table 6).

Example 29 Comparative

A modified catalyst support as described in Example 25, was prepared,but no post impregnation calcination step was performed (see Table 6).

Example 30 Inventive

A modified catalyst support as described in Example 29, was prepared,but with 5 vol % water in the total solvent mixture i.e. in theimpregnating liquid medium which thus comprised ethanol, acetic acid andwater (see Table 6).

Example 31 Comparative

Pural (boehmite phase alumina) was modified with Si, using TEOS (silicontetraorthosilicate) in ethanol as an impregnating liquid medium. TEOSwas added to the ethanol (see Table 6) and stirred for 10 minutes at 60°C. Pural was added to this mixture and stirred for another 10 minutes at60° C. The solvent was slowly removed with a gradual decrease in thepressure from atmospheric pressure to 80 mbar and maintaining it at 80mbar until dryness, while the temperature was maintained at 60° C. Bymeans of calcination at 550° C. for 2 hours in air, the modifyingcomponent containing catalyst support material was thus converted to acalcined modified catalyst support (Table 6).

Example 32 Inventive

A modified catalyst support as described in Example 31, was prepared,but with 5 vol % water in a solvent mixture of ethanol and water i.e. inan impregnating liquid medium which thus comprised ethanol and water(see Table 6).

Example 33 Comparative

Pural (boehmite phase alumina) was calcined at 550° C. for 2 hours andwas not modified at all.

Example 34 Comparative

Titania (spray dried and calcined at 550° C. for 2 hours) was modifiedwith Si, using TEOS (silicon tetraorthosilicate) dissolved in ethanol.TEOS was added to the ethanol (see Table 6) and stirred for 10 minutesat 60° C. Titania was added to this mixture and stirred for another 10minutes at 60° C. The solvent was slowly removed with a gradual decreasein the pressure from atmospheric pressure to 80 mbar and maintaining itat 80 mbar until dryness, while the temperature was maintained at 60° C.By means of calcination at 550° C. for 2 hours in air, the modifyingcomponent containing catalyst support material was thus converted to acalcined modified catalyst support (see Table 6).

Example 35 Inventive

A modified catalyst support as described in Example 34, was prepared,but with 19 vol % acetic acid and 5 vol % water in the total solventmixture, i.e. in an impregnating liquid medium which thus comprisedethanol, acetic acid and water (see Table 6).

Example 36 Comparative

Titania (spray dried and calcined at 550° C. for 2 hours), was notmodified at all.

TABLE 6 M- Delta Water Target utilisation D₁₀ Example Support (vol %)Metal wt % M (%) (μm) Ex 23 Al₂O₃ 0 Ti 2.6 84 5.8 (comparative) Ex 24Al₂O₃ 5 Ti 2.6 89 4.0 (inventive) Ex 25 Al₂O₃ 0 Si 1.6 70 3.8(comparative) Ex 26 Al₂O₃ 5 Si 1.6 83 3.2 (inventive) Ex 27 Al₂O₃ 0 Zr2.6 99 7.5 (comparative) Ex 28 Al₂O₃ 10  Zr 2.6 99 4.9 (inventive) Ex 29Al₂O₃ 0 Si 1.6 84 5.2 (comparative) Ex 30 Al₂O₃ 5 Si 1.6 99 3.1(inventive) Ex 31 boehmite 0 Si 2.4 81 8.5 (comparative) Ex 32 boehmite5 Si 2.4 87 6.2 (inventive) Ex 33 boehmite — — — — 10.5 (comparative) Ex34 TiO₂ 0 Si 1.6 80 1.5 (comparative) Ex 35 TiO₂ 5 Si 1.6 92 1.0(inventive) Ex 36 TiO₂ — — — — 7.1 (comparative)

The metal utilization and the delta D10 values were determined in thesame manner as described in Example 13

Example 37

The cumulative Al dissolution as a function of time was tested as perprocedures of Example 14 for samples from Examples 12, 23, 24, 29 and 30(see FIG. 4).

Example 38 Comparative

A cobalt catalyst precursor was prepared in the same manner as describedin Example 20, except that the support of Example 23 was used.

Example 39 Inventive

A cobalt catalyst precursor was prepared in the same manner as describedin Example 20, except that the support of Example 24 was used.

Example 40 Comparative

A cobalt catalyst precursor was prepared in the same manner as describedin Example 20, except that the support of Example 12 was used. TEOSmodification, using the procedure according to Example 25, wasperformed, except that no calcination at 550° C. was executed.

Example 41 Inventive

A cobalt catalyst precursor was prepared in the same manner as describedin Example 20, except that the support of Example 12 was used. TEOSmodification, using the procedure according to Example 26, wasperformed, except that no calcination at 550° C. was executed.

TABLE 7 Water (vol %) used Metal Target during used for wt % of Delta Alsupport support support D₁₀ of leach- modifi- modifi- modifying catalysting Example Support cation cation metal (μm) (ppm) Ex 38 Al₂O₃ 0 Ti 2.64.7 89 (compar- ative) Ex 39 Al₂O₃ 5 Ti 2.6 3.0 11 (inven- tive) Ex 40Al₂O₃ 0 Si 1.6 4.6 58 (compar- ative) Ex 41 Al₂O₃ 5 Si 1.6 3.0 19(inven- tive)

The invention claimed is:
 1. A method of preparing a modified catalystsupport, the method comprising: contacting a catalyst support materialwith a modifying component precursor in an impregnating liquid mediumwherein the impregnating liquid medium comprises a mixture of water andan organic liquid solvent for the modifying component precursor, whichmixture contains at least 2.5% by volume water, but less than 12% byvolume water based on the total volume of the impregnating liquidmedium, the catalyst support material is selected from the groupconsisting of a catalyst support precursor which is convertible to acatalyst support upon calcination thereof, the catalyst support being inthe form of a metal oxide which is an oxide of a metal selected from thegroup consisting of Al, Si, Ti, Mg, Zr and Zn; and a catalyst supportselected from the group consisting of alumina in the form of one or morealuminium oxides, silica (SiO₂), titania (TiO₂), magnesia (MgO),zirconium oxide (ZrO₂), zinc oxide (ZnO) and mixtures thereof; and themodifying component precursor comprises a compound of a modifyingcomponent selected from the group consisting of Si, Zr, Ti, Cu, Zn, Mn,Ba, Ni, Al, V, W, La and mixtures of two or more thereof, thereby toobtain a modifying component containing catalyst support material; andoptionally, calcining the modifying component containing catalystsupport material at a temperature above 100° C. to obtain a modifiedcatalyst support.
 2. The method according to claim 1 wherein theimpregnating liquid medium contains not more than 10% by volume water.3. The method according to claim 1, wherein the organic liquid solventcomprises a liquid organic compound which includes at least oneheteroatom selected from oxygen or nitrogen.
 4. The method according toclaim 3, wherein the heteroatom of the liquid organic compound of theorganic liquid solvent is oxygen, with the oxygen containing liquidorganic compound being an alcohol.
 5. The method according to claim 4wherein the liquid organic compound of the organic liquid solvent isethanol.
 6. The method according to claim 3 wherein the heteroatom ofthe liquid organic compound of the organic liquid solvent is nitrogen,with the nitrogen containing liquid organic compound being acetonitrile.7. The method according to claim 3 wherein the organic liquid solventcomprises a mixture of liquid organic compounds.
 8. The method accordingto claim 1, wherein the modifying component precursor includes one ormore organic groups bound to the modifying component.
 9. The methodaccording to claim 1 wherein, by contacting the catalyst supportmaterial with the modifying component precursor in the impregnatingliquid medium, the modifying component precursor is thus introduced intoand/or onto the catalyst support material by means of impregnation.